Ethers of glucosides



Patented Mar. 18, 1941 UNITED STATES PATENT OFFICE ETHERS OF GLUCOSDES poration of Michigan No Drawing. Application September 13, 1939, Serial No. 294,679

Claims.

This invention relates to the preparation of new and useful glucose derivatives.

It is an object of this invention to obtain glucose derivatives from ethylated complex polysaccharides.

A .further obj-ect is the preparation of glycosides of glucose others having substituent groups in two or more of :the 2, 3 land 6 positions ot the glucose residue `and the separation of the oli-substituted g-lycoside others from the tri-substituted derivatives.

Another object is the preparation of ethyl glucosides of 2.3.6-tri-substituted glucose others and of mixtures of ethyl -glucosides of 2.3-, 2.6-, and 3.6-di-substituted glucose -ethers substantially uncontaminated by other materials.

Yet `further objects will become apparent in the following description.

I attain these objects by carrying out a process of lalooholysis on :a highly ethylated comfplex polysaccharide and obtaining the desired substances from the mixed glucosidic products. The process of alcoholysis, especially when commercial polysaccharide ethers such as ethyl cellulose are used, will normally give a mixture of products. Etherificaltion of the polysaccharide is usually not uniform. Thus, a highly etherified ethyl cellulose, other than akcompletely etheniiie'd product, will yield on coholysis chieily :a triethyl glucoside. It will yield, in addition, quantities of .both diand mono-ethyl glucosides `besides unethylated glucoside and tars which almost'l invariably result from lprolonged heating of carbohydrate derivatives with acids. The problem oi isolating the diland tri-ethyl glucosides `from the reaction mixture and :their separation from each other is diiiicuit.y Fractional distillation is complicated by the number of the constituents and their chemical and physical similarity. Further, the presence of tars causes `an accelerated rate of decomposition o-n heating, It is desirable, therefore, to eiect a separation which avoids direct fractional distillati-on and its concomitant heating.

yAccording 'to the new process, the vpro-duct of alcoholysis @carried out by heating a complex polysaccharide ethyl ether with 3 to 6 times its weight of :a lower alcohol containing 2 to 4 carbon atoms in the ypresence of a catalytic quantity of va mineral acid in the manner Vdescribed in my co-pending application Serial No. 294,678, filed concurrently herewith) is extracted with a lower lpetnoleum fraction. I have found that the alkyl diand tri-ethyl glucosides, where alkyl is a radical containing 2 to 4 carbon atoms, are

(Cl. 260-2l0) soluble in lower aliphatic hydrocarbon solvents While the corresponding mono-ethyl derivatives, the unethylated derivatives and :the main part of the reaction tars are insoluble in these solvents. This discovery is surprising in view of 5 the fact that methyl 2.3.6-tri-methyi glucoside and methyl dimethyl glucosides having long been known to be insoluble in :aliphatic hydrocarbons. Following this partition by extraction, the .diand tri-ethyl glucosides may be separated by fnaclo tional ydistllation or by conventing them into the corresponding diand ltri-ethyl glucoses, separating the latter .by crystallization and reconventing .the separated component-s into glucosides, wherein the glucosidic group may consist of one or the following radicals:-alky=l radicals having 3 to 20 carbon atoms, and hydroxy-alkyl, alim-xyalkyl radicals derived from the corresponding alcohols. Other glucosides, preparalole from other alcohols of partially aromatic character, are described in a co-rlled application, Serial No. 294,680.

The new method of separation makes possible the isolati-on of the diand tri-ethyl gl-ucosides,

which, .on account of their good solubility propenties, compatibility and low volatility are valuable, permanent constituents of cellulose ether compositions. They :are also particularly valuable intermediates in the preparation of technically important serbi-tol others. The method is limited to the separation of the products of alcoholysis -when the reacting alcohol is ethyl alcohol, primary or secondary propyl alcohol, or primary or secondary butyl alcohols. The products of the `separation may be listed as follows: ethyl diand tri-ethyl Iglucos-ides, n-propyl diand tri-ethyl glucosides, sec-propyl diand triethyl glucosides, n-butyl diand tri-ethyl glucosdes, isobutyl diand tri-ethyl glucosides, and sec-butyl diand tri-ethyl g-luoosides.

In addition, the invention has .a valuable application in the preparation of 2.3.6-triethyl glucose and of mixed diethyl glucoses from which Ia wide variety of useful glucosides may be made. To this end, the isolated triand di-ethyl glu- 5 corses are heated with a `prin/lary or secondary alcohol .type compound of aliphatic character in :the `presence ot a mineral acid. A wide variety of such alcohol type compounds are available, namely, alkanols containing 3 .to 20 carbon atoms, 50 hydroxy-lallcanols, and alkoxy-alkanols. Examples of compounds of these types are butyl alcohol, glycerine, and ethoxy ethyl alcohol. This list may be extended indefinitely.

The invention has particular utility in the sepfaration of lower alkyl diand tri-ethyl gluoosi'des jfrom products of alcoholysis of .commercial ethyl vcellulose, since technical ethyl cellulose of sufficiently high etlroxy content to yield high proportions of diand tri-ethyl glucosides is readily available. The new ethyl ethers of glucosides have the general formula mit barium carbonate and the precipitated barium sulphate removed by ltration. The ltrate is evaporated under reduced pressure to crystallization. Upon formation of crystals, the ask is removed from its bath, heated to dissolve the crystals already formed and allowed to cool. The crystalline product is removed from its mother liquor, pressed dry and recrystallzed from distilled water. The mother liquor and washings are then further evaporated and set lil aside to crystallize. Repetition of this process frees the liquor of most of the tri-derivative which upon recrystallization from Water is obtained pure. Melting point 94-95 C. and the Il l.

EXAMPLE Preparation of heta-ethoy ethyl 2.3.6-trz'ethyl glucoside This preparation is carried out as in Example 3, lauryl alcohol being replaced by an identical volume of cellosolve (monoethyl ether of ethylene glycol). The product is a colorless, mobile liquid boiling at 160 C. under 2 mm. pressure and of refractive index 1.4505 at 25 C.

The new compounds are useful as intermediates in the preparation of novel sorbitol ethers and as plasticizers, softening agents, and the like, particularly in cellulose ether compositions.

I claim:

l. In a method of preparing a lower alkyl 2.3.6- triethyl glucoside and of mixed lower alkyl 2.3-, 2.6- and 3.6-diethyl glucosides from an ethylated complex polysaccharide, the step of separating a mixture of lower alkyl 2.3.6-triethy1 glucoside and lower alkyl 2.3-, 2.6- and 3.6-diethyl glucosides from lower alkyl mono-ethyl glucosides, lower alkyl unethylated glucoside and reaction tars by extraction with petroleum ether, the lower alkyl group in each instance derived from a primary or secondary alcohol containing 2 to 4 carbon atoms inclusive.

2. In a method of preparing a lower alkyl 2.3.6- triethyl glucoside and of mixed lower alkyl 2.3-, 2.6- and 3.6-diethyl glucosides from ethyl cellulose, the step of separating a mixture of lower alkyl 2.3.6-triethyl glucoside and lower alkyl 2.3-, 2.6- and 3.6-diethyl glucosides from lower alkyl mono-ethyl glucosides, lower alkyl unethylated glucoside and reaction tars by extraction with petroleum ether, the lower alkyl group in each instance derived from a primary or secondary alcohol containing 2 to 4 carbon atoms inclusive.

3. In a method of preparing a lower alkyl 2.3.6- triethyl glucoside and of mixed lower alkyl 2.3-, 2.6- and 3.6-diethyl glucosides from ethyl starch, the step of separating a mixture of lower alkyl 2.3.6-triethyl glucoside and lower alkyl 2.3-, 2.6- and 3.6-diethyl glucosides from lower alkyl monoethyl glucosides, lower alkyl unethylated glucose and reaction tars by extraction with petroleum ether, the lower alkyl group in each instance derived from a primary or secondary alcohol containing 2 to 4 carbon atoms inclusive.

4. A method of separating lower alkyl 2.3.6- triethyl glucosides and mixed lower alkyl 2.3-, 2.6- and 3.6-diethyl glucosides from the product of alcoholysis of an ethylated complex polysaccharide using a primary or secondary alcohol of 2 to 4 carbon atoms, which comprises extracting the alcoholic reaction product with petroleum ether and recovering said triand diethyl glucosidic compounds from solution in said solvent.

5; In a method of preparing a 2.3.6-triethyl glucoside and o-f mixed 2.3-, 2.6- and 3.6-diethyl glucosides from an ethylated polysaccharide, the steps which comprise heating the ethylated polysaccharide with 3 to 6 times its weight o1 a primary or secondary lower monohydric aliphatic alcohol containing 2 to 4 carbon atoms in the presence of a catalytic amount of a mineral acid, extracting the product or this alcoholysis with petroleum ether, recovering a mixture of lower alkyl' 2.3.6-triethyl glucoside, and lower alkyl 2.3-, 2.6- and 3.6-diethyl glucosides by evaporation `of the petroleum ether extract, hydrolyzing this mixture by heating with an aqueous solution of a mineral acid to form 2.3.6-triethyl glucose and 2.3-, 2.6- and 3.6-diethyl glucoses, separating the 2.3.6-triethyl glucose from the diethyl derivatives by crystallization followed by extraction with chloroform, and converting the so-separated glucose ethers into glucosides by heating with an alcohol type body of aliphatic nature selected from the group consisting of alkanols containing 3 to 20 carbon atoms, hydroxy-alkanols, and alkoxy-alkanols, in contact with mineral acid.

6. A new compound having the general formula l H-o-o n, I Rao-C-H o H- on H l H2O-o n,

wherein R1 is selected from the class consisting of alkyl groups containing from 3 to 20 carbon atoms, inclusive, hydroxy-alkyl radicals, and alkoxy-alkyl radicals, and R2 is selected from the class consisting of ethyl and hydrogen, a pluthe groups designated as Rz are ethyl, the remainder being hydrogen.

9. A new compound having the general formula wherein the groups designated as R are selected from the class consisting of hydrogen and ethyl, a plurality of them being ethyl.

10. A new compound having the general formula 02H, o on, cih-0 CH\ rr- -oR l wherein, the groups designated as R are selected from the class consisting of ethyl and hydrogen, a plurality of them being ethyl.

ELWOOD V. WHITE. 

